Poly-perfluoroalkyl-substituted alcohols and acids, and derivatives thereof

ABSTRACT

Di-, tri- and poly-perfluoroalkyl-substituted alcohols and acids and derivatives thereof are described which are prepared from perfluoroalkyl iodides and di-, tri- or polyallyl alcohols or acids. These compounds contain two or more perfluoroalkyl-iodoalkyl or perfluoroalkyl-alkenyl groups and one or two alcohol or acid groups or derivatized alcohol or acid functions. They can be reacted with isocyanates, epoxy compounds, anhydrides, acids or acid derivatives to prepare a great variety of oil- and water-repellent compositions which are useful for oil- and water-repellent treatment of textiles, glass, paper, leather and other substrates.

This is a division of Ser. No. 08/270,083, filed Jul. 1, 1994 now U.S.Pat. No. 5,491,261.

BACKGROUND OF THE INVENTION

Perfluoroalkyl-substituted polymers possess free surface energies evenlower than that of polytetrafluoroethylene. They have therefore longbeen used to impart oil- and water repellency to a wide variety ofsubstrates, especially textiles. Additionally, phosphate esters ofperfluoroalkyl-substituted alcohols are being used as oil- andwater-repellent paper sizing, for instance in paper plates and in foodpackaging products. For such applications, it is especially importantthat the paper sizing compound contain at least 2 R_(F) -groups, whereR_(F) is a perfluoroalkyl group. When mono-R_(F) -alcohols are used toesterify phosphoric acid, only the diesters are active oil- andwater-repellents; the monoester is too water soluble and, even ifretained on the cellulose fiber, reduces water repellency, and thetriester is not substantive. Making phosphate diesters in high yield is,however, very difficult in practice; substantial amounts of mono- andtriesters are always produced as by-products.

Typical fluorinated mono-alcohols are perfluoroalkyl-alkanols, such as3-perfluoroalkyl-propene-2-ol. See J. Fluorine Chem., 20(3), 313-27(1982), DE 23 33 935 (1974), DE 22 55 672 (1973) and FR 1 473 451(1967). Such monofunctional alcohols, while suitable for the preparationof acrylic and methacrylic oil- and water-repellent R_(F) -polymers, areless suitable for the preparation of oil- and water-repellent phosphateesters for reasons given above. Likewise, it is also impossible toprepare oil- and water-repellent sulfuric acid half esters frommono-R_(F) -alcohols since such esters are very water soluble anionicsurfactants. For the preparation of oil- and water-repellentpolyurethanes it is especially important that the diol contain more thanone R_(F) group.

Using di-R_(F) -alcohols makes it possible to prepare oil- andwater-repellent phosphate or sulfate monoester paper sizes, since even amonoester contains two R_(F) -groups. Certain di-R_(F) -diols aredescribed in U.S. Pat. Nos. 3,935,277 and 4,946,992. Said patentsdescribe the synthesis of di-R_(F) -alcohols and diols by reaction ofR_(F) -ethylenethiol with halogenated alcohols and diols.

Polyurethanes of di-R_(F) -diols are described in U.S. Pat. Nos.3,968,066, 4,046,944, 4,054,592 and 4,098,742. Phosphate esters aredescribed in U.S. Pat. Nos. 5,091,550 and 5,132,445. Although thedi-R_(F) -phosphates show excellent performance, their synthesisinvolves many steps and costly intermediates. Similar compounds producedby a more straightforward synthesis route and preferably lacking thethermally unstable thioether linkage would be highly desirable.

It has now been discovered that di-, tri- andpoly-perfluoroalkyl-substituted alcohols which fulfill theserequirements can be prepared in high yields from perfluoroalkyliodidesand di-, tri- or polyallyl alcohols or acids. These compounds have notpreviously been described. They are useful by themselves or asintermediates for making end products which impart outstanding oil andwater repellency to textiles, paper, leather, wood and other substrates.

Sugar derived perfluoroalkyl substituted polyols have been synthesizedearlier, namely from xylitol, galactose, and glucose; see Bull. Soc.Chim. Fr., 872-8 (1989), J. Med. Chem., 33(4), 1262(1990) and U.S. Pat.No. 4,985,550. Such polyols, with a hydroxyl functionality of three ormore, are not suitable for preparing linear polymer compositions sincecrosslinking is likely to occur.

DETAILED DISCLOSURE

This invention describes di- tri- and oligoperfluoroalkyl-substitutedmono- and dialcohols, mono- and diacids and derivatives thereof, andmethods for making them. Other aspects of this invention relate to thereaction products of oligoperfluoroalkyl alcohols with isocyanates,epoxides, acids, acid chlorides, and anhydrides.

Another aspect of this invention relates to a substrate containing 0.01to 10% by weight of an organofluorine-containing composition, at leastpart of said fluorine being provided by one or more units derived froman inventive oligoperfluoroalkyl substituted alcohol, acid, or aderivative thereof.

The novel oligo-perfluoroalkyl alcohols and acids are of the formulae Ior II

    (Q.sub.F --CH.sub.2 O).sub.b --Y--(X).sub.a (I) or Z.sub.e (--L--(U--OH).sub.d).sub.c                                (II)

wherein

Q_(F) is Q_(F1) or Q_(F2), in which Q_(F1) is R_(F) CH₂ CHI-- and Q_(F2)is R_(F) CH═CH--, and R_(F) is a monovalent, perfluorinated, alkyl oralkenyl, straight, branched or cyclic organic radical having three totwenty fully fluorinated carbon atoms, which radical can be interruptedby divalent oxygen or sulfur atoms, with each R_(F) radical beingidentical or different from the other R_(F) radicals,

Y is a trivalent or tetravalent organic linking group with from 1 to 20carbon atoms, which can be interrupted by one or more polyvalent groupsor hetero atoms selected from --O--, --S--, --N<, --NR₁ --, --CO--,--CONR₁ --, --NHCOO--, --CON<, --CO₂ --, --O₂ C--, --O₂ CO-- and --SO₂--, in which

R₁ is hydrogen, C₁ -C₂₀ alkyl, di-C₁ -C₂ alkylamino-C₂ -C₆ alkylene,hydroxy-C₁ -C₅ alkylene, or C₁ -C₅ alkyl or hydroxy-C₁ -C₅ alkylenewhich is substituted by pyridyl, piperidyl or cyclohexyl,

X is OH, O--CH₂ --COOH or COOH,

a is 1 or 2,

b is 2 or 3,

L is O, S or NR', in which

R' is C₁ -C₂₀ hydrocarbyl, hydroxy-C₂ -C₅ alkylene, carboxymethylene orU--OH,

U is ##STR1##

Z is H or a mono-, di-, tri- or tetravalent organic group of 1-40 carbonatoms which can be interrupted by one or more polyvalent groups orhetero atoms selected from --O--, --S--, --N<, --NR₁ --, --CO--, --CONR₁--, --NHCOO--, --CON<, --CO₂ --, --O₂ C--, --O₂ CO-- and --SO₂ --, andcan also be substituted by hydroxyl, carboxyl, carboxyalkyl or sulfonatewhen L is S or NR',

r and q are each, independently, 0 to 10,

c is 1 to 4,

d is 1 to 3, with the proviso that when c and d are both 1, Z ismonovalent and r is >0, and

e is 0 or 1, with the proviso that when e is 0, d is 2 and L is S orNR'.

The alkyl and alkylene groups encompassed by Y, Z, R₁ and R' can belinear, branched or carbocyclic, including phenylene. The termhydrocarbyl includes alkyl, alkenyl, aryl and alkaryl.

Preferred are compounds of the formulae I and H wherein Q_(F) is Q_(F2)and R_(F) is saturated, contains 6-18 carbon atoms, is fully fluorinatedand contains at least one terminal perfluoromethyl group. Mostpreferably, R_(F) is a fully fluorinated, linear carbon chain with 6 to14 carbon atoms.

Preferred compounds of the formula I are those wherein Y is a trivalentor tetravalent hydrocarbyl linking group with from 2 to 10 carbon atoms.

Preferred alcohols of the formula I (X=OH) of this invention are (Q_(F2)CH₂ OCH₂)₂ CHOH, (Q₂ CH_(F2) OCH₂)₂ C(CH₂ OH)₂, (Q_(F2) CH₂ OCH₂)₃C--CH₂ OH and (Q_(F2) CH₂ OCH₂)₂ C(C₂ H₅)CH₂ OH. The last two areespecially preferred.

Typical examples of acids of the formula I (X=COOH) of this inventioninclude ##STR2##

Also useful are amino acids obtained by reaction of mono- or diaminoacids with allyl chloride or allyl bromide, for example the compound offormula ##STR3## where Q_(F) is as defined above, which is obtained byreaction of ethylenediamine diacetic acid (EDDA) with allyl chloride.

Preferred compounds of the formula II are those wherein Q_(F) is Q_(F2)and R_(F) is saturated, contains 6-18 carbon atoms, is fully fluorinatedand contains at least one terminal perfluoromethyl group, r is equal toor greater than q and the sum of r plus q is 0 to 10. Most preferablyR_(F) is a fully fluorinated, linear carbon chain with 6 to 14 carbonatoms, r is is equal to or greater than q and is 0 to 5 and q is 0 to 3.

In one preferred embodiment, L is O, c and d are 1 and Z is phenyl,carboxyphenyl, p-n-C₁ -C₁₀ alkylphenyl, a monovalent alkyl or alkenylradical with 1-20 carbon atoms which may be interrupted by --O--, --S--or --NR₁ -- groups, and may be substituted by one or two carboxylgroups, or is hydroxy-C₂ -C₅ alkylene, such as the monoradical residue(minus 1 OH group) of ethanol, propanol, butanol, isopropanol, decanol,10,11-undecenol, ethylene glycol, N,N-dimethylaminopropanol,p-hydroxybenzoic acid, phenol or p-octylphenol.

In another preferred embodiment, L is O, c is 2, d is 1 and Z is1,4-phenylene or a divalent alkylene radical which may be interrupted by--O--, --S-- or --NR₁ -- groups and substituted by one or two carboxylgroups. Typical examples of Z are the radical residues of glycols orpolyols (minus 2 OH groups) such as those of ethylene glycol, propyleneglycol, hexylene glycol, polyoxyethylene glycols, i.e. --(CH₂ CH₂ O)_(n)CH₂ CH₂ -- where n is 2-20, hydroquinone, glycerol, trimethylolpropane,2,2-bishydroxymethylpropionic acid methyl ester, N-methyldiethanolamine,triethanolamine, 3-(diethylamino)-1,2-propanediol and of alkoxylated andpolyalkoxylated primary or bis-secondary amines, with --CH₂ CH₂ -- andCH₃ N(CH₂ CH₂ --)₂ being preferred.

In another preferred embodiment, L is O, c is 3, d is 1 and Z is atrivalent alkylene radical which may be interrupted by --O--, --S-- or--NR₁ -- groups. Examples are the triradical residue of a polyol (minus3 OH groups), such as CH₃ CH₂ C(CH₂ --)₃ (from trimethylpropane) or--CH(CH₂ --)₂ (from glycerol), and of alkoxylated and polyalkoxylatedprimary aminoalkanols.

In another preferred embodiment, L is O, c is 4, d is 1 and Z is atetravalent residue of a polyol (minus 4 OH groups), such as frompentaerythritol, i.e. C(CH₂ --)₄,N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine,N,N,N'N'-tetrakis(2-hydroxyethyl)ethylenediamine or polyalkoxylateddiprimary diamines.

In another preferred embodiment, L is S, d is 2 and Z is either a directbond if e is 1 or e is 0.

In another preferred embodiment, L is S, d and c are 1 and Z is amonovalent linear or branched alkyl radical with 1-20 carbon atoms,hydroxy-C₂ -C₅ alkylene, carboxy-C₂ -C₄ alkylene or --CH(COOH)CH₂ COOH,with --CH₂ CHOHCH₂ OH, --CH₂ CH₂ COOH and --CH(COOH)CH₂ COOH beingpreferred.

In another preferred embodiment, L is S, d is 1, c is 2 and Z is adivalent C₂ -C₂₀ -alkylene radical which may be interrupted by --O-- or--NR₁ --.

Alcohols of formula II of this invention also include those wherein L isNR', in which R' is U--OH, C₁ -C₅ alkyl or carboxymethylene, c, d and eare each 1 and Z is monovalent.

When L is NR', in which R' is U--OH, Z is preferably a monovalent alkylradical with 1-20 carbon atoms which may be interrupted by --O--, --S--or --NR₁ -- groups or a phenyl radical, which radicals may besubstituted by hydroxy, carboxy or sulfonate groups. Z is mostpreferably the radical residue (minus 1 NH₂) of butylamine,aminoethanol, 1,1 -dihydroxymethylaminopropane,tris(hydroxymethyl)aminomethane, glucamine, p-aminobenzoic acid,beta-alanine or HOOC--CH(NH₂)--A, wherein A is the radical residue of ana-amino acid such as glycine, alanine, aspartic acid, glutamic acid ormurine.

In alcohols of formula II wherein L is NR' and R' is U--OH, Z asHOOC--CH₂ CH₂ --, HOOC--CH₂ --, HOOC--CH(CH₃)--, --CH₂ CH₂ SO₃ H,--CH(COOH)--(CH₂)₁₋₂ COOH, --C(C₂ H₅)(CH₂ OH)₂ and (CH₃)₂ N(CH₂)₃ -- aremost especially prefered.

When L is NR', in which R' is C₁ -C₅ alkyl or carboxymethylene, Z ismost preferably the radical residue (minus 1 NHR₁) of a secondary amine,such as diethanolamine, dibutylamine, N-methyltaurine or sarcosine.

In other embodiments, L is NR', c is 2 to 4, d is 2 and R' is U--OH, ord is 1 and R' is alkyl with 1-5 carbon atoms or a carboxymethylenegroup, and Z is a divalent alkylene radical with 2 to 12 carbon atomswhich can be interrupted by --O--, --S-- or --NR₁ -- groups andsubstituted by hydroxy, carboxy or sulfonate groups. Typical examples ofZ are the diradical residues (minus 2 NH₂ or NHR₁ groups) of diprimaryamines, disecondary amines or primary-secondary amines, such as those of1,3-diaminopropane, 1,3-diamino-2-hydroxypropane,2-(2-aminoethylamino)-ethanol, N,N'-bis(2-hydroxyethyl)-ethylenediamine,ethylenediamine diacetic acid and lysine, withN,N'-bis(2-hydroxyethyl)ethylenediamine and ethylenediamine diaceticacid being preferred.

Preferred alcohols of the formula II of this invention include (Q_(F2)CH₂ OCH₂ CH(OH)CH₂)₂ N--C(CH₂ OH)₂ C₂ H₅, (Q_(F2) CH₂ OCH₂ CH(OH)CH₂)₂S, (Q_(F2) CH₂ OCH₂ CH(OCH₂ CH₂ OH)CH₂)₂ S and Q_(F2) CH₂ OCH₂CH(OH)CH(OH)CH₂ OCH₂ Q_(F2).

The alcohols and diols of this invention can be used to make a varietyof products such as esters, ether-alcohols, carbonates, carboxylicacids, phosphates, sulfates and urethanes, which are other objects ofthis invention. Preferred are derivatives of the alcohols and diolswhere Q_(F) is Q_(F2).

Among the preferred esters are those of the formulae Ia and IIa

    (Q.sub.F2 CH.sub.2 O).sub.b --Y--(O.sub.2 C--R.sub.3).sub.a (Ia) and Z(--L--O.sub.2 C--R.sub.3).sub.d).sub.c                   (IIa)

wherein Q_(F2), Y, a, b, Z, L, U, d and c are as defined above and R₃ isH or C₁ -C₂₀ hydrocarbyl, which may be substituted by one or morehydroxyl, thiol or carboxyl groups. Typical examples of --O₂ C--R₃include the radicals of acetic, benzoic, hydroxybenzoic, terephthalic,phthalic, acrylic, methacrylic, citric, maleic, fumaric, itaconic,malonic, succinic, thioacetic, thiopropionic and thiosuccinic acids.Addition polymers may be derived from the acrylates, methacrylates orfumarates.

Preferred esters of the formula Ia are acrylates, methacrylates,maleates, fumarates, succinates and ortho- and terephthalates of thealcohols of the formulae (Q_(F2) CH₂ OCH₂)₂ CHOH, (Q_(F2) CH₂ OCH₂)₂C(CH₂ OH)₂, (Q_(F2) CH₂ OCH₂)₃ C--CH₂ OH and (Q_(F2) CH₂ OCH₂)₂ C(C₂H₅)CH₂ OH, wherein Q_(F2) is as defined above.

Also preferred are acrylates, methacrylates, maleates, fumarates,succinates and ortho- and terephthalates of diols of the formulae IIband IIc

    Z.sub.e --N--(U--OH).sub.2 (IIb) and Z.sub.e --(O--U--OH).sub.2(IIc),

wherein, in the definition of U, r is equal to or greater than q and is0 to 5, q is 0 to 3 and, when e is 1, Z is a monovalent hydrocarbylradical with 1-20 carbon atoms which may be interrupted by --O--, --S--or --NR₁ -- and may be substituted by hydroxy or carboxy groups, or,when e is 2, Z is 1,4-phenylene or a divalent alkylene radical which maybe interrupted by --O--, --S-- or --NR₁ -- groups, wherein R₁ is asdefined above. Most preferably, Z is a monovalent alkyl radical with1-18 carbon atoms or is --CH₂ CH₂ --.

Also useful are polyesters of the formulae Id and IId ##STR4## wherein Yis a tetravalent organic linking group with from 2 to 20 carbon atoms, Zis a divalent alkylene radical with 2 to 12 carbon atoms which can beinterrupted by --O--, --S-- or 1,4-phenylene and substituted by 1 or 2carboxyl groups, n is an integer from 2 to 100, preferably 3 to 10,Q_(F2), U, and L are as defined above and R₄ is the divalent radicalresidue of a dicarboxylic acid of the formula HOOC--R₄ --COOH.

R₄ is preferably a direct bond, an alkylene of 1-16 carbon atoms, anarylene of 6 to 14 carbon atoms or an alkarylene of 7 to 18 carbonatoms. Such acids include oxalic, malonic, succinic, glutaric, adipic,pimelic, suberic, azelaic, sebacic, brassylie, octadecanedioic, dimeracid, 1,4-cyclohexanedicarboxylic, 4,4'-dicyclohexyl-1,1'-dicarboxylic,phthalic, isophthalic, terephthalic, methylphthalic,diphenyl-2,2'-<dicarboxylic, diphenyl-4,4'-dicarboxylic, 1,4-naphthalenedicarboxylic, diphenylmethane-2,2'-dicarboxylic,diphenylmethane-3,3'-dicarboxylic, diphenylmethane-4,4'-dicarboxylicacid and the like. Also useful are compounds wherein R₄ is substitutedby one or two carboxy groups and is derived, for example, frompyromellitic anhydride or benzene tetracarboxylic acid dianhydride.

Especially preferred are polyesters of the formula Id wherein Y is --CH₂(CH--)CH₂ --S--CH₂ (CH--)CH₂ -- or --CH₂ (CH--)CH₂ --NR'--CH₂ (CH--)CH₂-- and R₄ is --CH═CH--, --(CH₂)₂₋₈ or 1,3- or 1,4-phenylene, andpolyesters of the formula IId wherein L is O, R_(l) is --CH═CH--,--(CH₂)₂₋₈ -- or phenylene, Z is a divalent alkylene radical which maybe interrupted by --O--, --S-- or --NR₁ -- groups and, in the definitionof U, r is equal to or greater than q and is 0 to 5 and q is 0 to 3.

Useful phosphates are the mono- and diphosphates and bis-monophosphatesof alcohols and polyols of the formulae I and II. Preferredmonophosphates of alcohols and polyols of the formula I are those fromalcohols and diols of the formulae (Q_(F2) CH₂ OCH₂)₂ CHOH, (Q_(F2) CH₂OCH₂)₂ C(CH₂ OH₂, (Q_(F2) CH₂ OCH₂)₃ C--CH₂ OH and (Q_(F2) CH₂ OCH₂)₂C(C₂ H₅)CH₂ OH, wherein Q_(F2) is as defined above.

Especially preferred are phosphates of alcohols and polyols of theformula I wherein Y is --CH₂ (CH--)CH₂ --S--CH₂ (CH--)CH₂ -- or --CH₂(CH--)CH₂ --NR'--CH₂ (CH--)CH₂ -- as well as phosphates of the formula##STR5## wherein Q_(F2) is as defined above.

Also preferred are monophosphates of diols of the formula II wherein, inthe definition of U, r is equal to or greater than q and is 0 to 5 and qis 0 to 3.

Also preferred are monophosphates of diols of the formula II wherein Uis as defined above, L is O and Z is phenyl, p-n-C₁ -C₁₀ alkylphenyl, amonovalent alkyl radical with 1-20 carbon atoms which may be interruptedby --O--, --S-- or --NR₁ -- groups, or is hydroxy-C₂ -C₅ alkylene.

Also preferred are monophosphates of diols of the formula II wherein Uis as defined above, L is O and Z is 1,4-phenylene or a divalentalkylene radical which may be interrupted by --O--, --S-- or --NR₁ --groups.

Also preferred are monophosphates of diols of the formula II wherein Uis as defined above, L is O and Z is a trivalent alkylene radical whichmay be interrupted by --O--, --S-- or --NR₁ --.

Also preferred are monophosphates of diols of the formula II wherein Uis as defined above, L is S and Z is a direct bond or a divalent C₂ -C₂₀alkylene radical which may be interrupted by --O-- or --NR₁ --.

Also preferred are monophosphates of diols of the formula II wherein Uis as defined above, L is NR', wherein R' is U--OH and Z is a divalentalkylene radical with 2 to 12 carbon atoms which can be interrupted by--O--, --S-- or --NR₁ -- groups and substituted by hydroxy or carboxygroups.

Most preferred are monophosphates of diols of the formula II wherein Uis as defined above, L is O and Z is --CH₂ CH₂ -- or CH₃ CH₂ C(CH₂ --)₃,and phosphates of the formula ##STR6## wherein Q_(F2) is as definedabove.

Useful sulfates are the mono- and disulfates of alcohols and polyols ofthe formulae I and II. Preferred monosulfates of alcohols and polyols ofthe formula I are those from alcohols and diols of the formulae (Q_(F2)CH₂ OCH₂)₂ CHOH, (Q_(F2) CH₂ OCH₂)₂ C(CH₂ OH)₂, (Q_(F2) CH₂ OCH₂)₃C--CH₂ OH and (Q_(F2) CH₂ OCH₂)₂ C(C₂ H₅)CH₂ OH, wherein Q_(F2) is asdefined above.

Also preferred are monosulfates of diols of the formula II wherein, inthe definition of U, r is equal to or greater than q and is 0 to 5 and qis 0 to 3.

Also preferred are monosulfates of diols and polyols of the formula IIwherein U is as defined above, L is O and Z is phenyl, p-n-C₁ -C₁₀alkylphenyl, a monovalent alkyl radical with 1-20 carbon atoms which maybe interrupted by --O--, --S-- or --NR₁ -- groups, or is hydroxy-C₂ -C₅alkylene.

Also preferred are monosulfates of diols and polyols of the formula IIwherein U is as defined above, L is O and Z is 1,4-phenylene or adivalent alkylene radical which may be interrupted by --O--, --S-- or--NR₁ -- groups.

Also preferred are monosulfates of diols and polyols of the formula IIwherein U is as defined above, L is O and Z is a trivalent alkyleneradical which may be interrupted by --O--, --S-- or --NR₁ -- groups.

Also preferred are monosulfates of diols and polyols of the formula IIwherein U is as defined above, L is S and Z is a direct bond or adivalent C₂ -C₂₀ alkylene radical which may be interrupted by --O-- or--NR₁ --.

Also preferred are monosulfates of diols and polyols of the formula IIwherein U is as defined above, L is NR', R' is U--OH and Z is amonovalent alkyl radical with 1 to 20 carbon atoms which be interruptedby --O--, --S-- or --NR₁ -- groups and substituted by hydroxy or carboxygroups.

The most preferred monosulfates of diols of the formula II are thosewherein U is as defined above, L is O and Z is --CH₂ CH₂ --, and thoseof the formulae CH₃ CH₂ --C--(CH₂ OCH₂ CH(OH)CH₂ OCH₂ Q_(F2))₃ and(HOCH₂)₂ (C₂ H₅)--C--N(CH₂ OCH₂ CH(OH)CH₂ OCH₂ Q_(F2))₂.

Useful polyurethanes consist of or contain units of the formulae Ie orIIe ##STR7## wherein Y, U and L are as defined as above, Z is a divalentradical as defined above and R₅ is the diradical residue of adiisocyanate of the formula OCN--R₅ --NCO.

Useful aromatic diisocyanates of the formula OCN--R₅ --NCO includetoluene diisocyanate (TDI) (all isomers), 4,4'-diphenylmethanediisocyanate (MDI), tolidine diisocyanate, dianisidine diisocyanate,m-xylylene diisocyanate, p-phenylene diisocyanate, m-phenylenediisocyanate, 1-chloro-2,4-phenylene diisocyanate,3,3'-dimethyl-4,4'-bisphenylene diisocyanate,4,4'-bis(2-methylisocyanatophenyl)methane, 4,4'-bisphenylenediisocyanate, 4,4'-bis(2-methoxyisocyanatophenyl)methane,1-nitrophenyl-3,5-diisocyanate, 4,4'-diisocyanatediphenyl ether,3,3'-dichloro-4,4'-diisocyanatodiphenyl ether,3,3'-dichloro-4,4'-diisocyanatodiphenyl methane,4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatediphenyl,2,2'-dimethyl-4,4'-diisocyanatodiphenyl,2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl,3,3'-dichloro-4,4'-diisocyanatodiphenyl, 1,2-naphthalene diisocyanate,4-chloro-1,2-naphthalene diisocyanate, 4-methyl-1,2-naphthalenediisocyanate, 1,5-naphthalene diisocyanate, 1,6-naphthalenediisocyanate, 1,7-naphthalene diisocyanate, 1,8-naphthalenediisocyanate, 4-chloro-1,8-naphthalene diisocyanate, 2,3-naphthalenediisocyanate, 2,7-naphthalene diisocyanate, 1,8-dinitro-2,7-naphthalenediisocyanate, 1-methyl-2,4-naphthalene diisocyanate,1-methyl-5,7-naphthalene diisocyanate, 6-methyl-1,3-naphthalenediisocyanate and 7-methyl- 1,3-naphthalene diisocyanate.

Useful aliphatic or cycloaliphatic polyisocyanates include 1,2-ethanediisocyanate, 1,3-propane diisocyanate, 1,4-butane diisocyanate,2-chloropropane-1,3-diisocyanate, pentamethylene diisocyanate,propylene-1,2-diisocyanate, 1,8-octane diisocyanate, 1,10-decanediisocyanate, 1,12-dodecane diisocyanate, 1,16-hexadecane diisocyanateand other aliphatic diisocyanates such as 1,3- and 1,4-cyclohexanediisocyanate.

Additionally, the following diisocyanates are particularly preferredbecause urethane compositions made therefrom tend to be non-yellowing:1,6-hexamethylene diisocyanate (HDI), 2,2,4- and2,4,4-trimethylhexamethylene diisocyanate (TMDI), dimer acid deriveddiisocyanate (DDD obtained from dimerized fatty acids such as linoleicacid, 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI),isophorone diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyldiisocyanate, lysine methyl ester diisocyanate (LDIM),bis(2-isocyanatoethyl) fumarate (FDI), bis(2-isocyanatoethyl) carbonateand m-tetramethylxylylene diisocyanate (TMXDI).

Preferred are polyurethanes of 3,000 to 30,000 molecular weight of theformula Ie and containing repeating units of the formulae ##STR8##wherein R₁ is C₁ -C₅ alkyl, R₅ is is the diradical residue of isophoronediisocyanate, 2,2,4-(2,4,4)-trimethylhexamethylene diisocyanate or1,6-hexamethylene diisocyanate and Q_(F2) is as defined above.

Also preferred are polyurethanes of 3,000 to 30,000 molecular weight andcontaining repeating units of the formula IIe wherein, in the definitionof U, r is equal to or greater than q and is 0 to 5, q id 0 to 3, U isas defined above, L is O, Z is --CH₂ CH₂ -- and R₅ is the diradicalresidue of isophorone diisocyanate, 2,2,4-(2,4,4)-trimethylhexamethylenediisocyanate or 1,6-hexamethylene diisocyanate.

Also preferred are polyurethanes of 3,000 to 30,000 molecular weight andcontaining units of the formula IIe wherein U is as defined above, L isS and Z is a direct bond.

Also especially preferred are polyurethanes of 3,000 to 30,000 molecularweight and containing units of the formula IIe wherein U is as definedabove, L is NR', wherein R' is C₁ -C₅ alkyl and Z is a divalent C₂ -C₁₂alkylene radical.

Also especially preferred are polyurethanes of 3,000 to 30,000 molecularweight and containing units of the formula IIe wherein U is as definedabove, L is NR', wherein R' is U--OH and Z is a monovalent radical with1 to 20 carbon atoms which be interrupted by --O--, --S-- or --NR₁ --groups.

It is within the scope of this invention to further react thesepolyurethanes with diisocyanates and polyisocyanates, or to incorporatethe novel R_(F) -diols into polyurethane resin systems to makecrosslinked polyurethanes, such as coatings or foams, as is known tothose skilled in the art of polyurethane chemistry.

Ether derivatives of the formula If are also useful

    (Q.sub.F2 CH.sub.2 O).sub.b --Y--(O--CH.sub.2 CH(OH)R.sub.6).sub.a(If)

wherein R₆ is hydrogen, a hydrocarbon radical with 2 to 20 carbon atoms,or a polyethylene oxide radical --(OCH₂ CH₂)_(u) --R₇, wherein R₇ is OHor (Q_(F2) CH₂)_(b) --Y--O--CH₂ CH(OH), u is an integer from 2 to 50 andQ_(F2), Y, a and b are as defined above.

Especially useful are ether acids of the formula I wherein X is O--CH₂--COOH and Q is Q_(F2), wherein Q_(F2), Y, a and b are as defined above.

It is understood that an R_(F) group usually represents a mixture ofperfluoroalkyl moieties. When the R_(F) group is identified as having acertain number of carbon atoms, said R_(F) group also usuallyconcomitantly contains a small fraction of perfluoroalkyl groups withfewer carbon atoms and a small fraction of perfluoroalkyl groups withmore carbon atoms. Commonly the perfluoroalkyl moiety is a mixture of C₄F₉, C₆ F₁₃, C₈ F₁₇, C₁₀ F₂₁, C₁₂ F₂₅, and C₁₄,F₂₉ groups.

The novel R_(F) -alcohols of this invention are obtained by the reactionof a perfluoroalkyl iodide with an allyloxy alcohol, to first yield aniodide compound wherein Q_(F) =Q_(F1), followed by dehydrohalogenationof the iodide with a base to yield an unsaturated alcohol with Q_(F)=Q_(F2). Useful commercial allyloxy alcohols are pentaerythritol di- andtriallyl ether and trimethylolpropane diallyl ether. Other alcohols canbe synthesized as follows: polyallyl ethers by reaction of triols,tetraols and of polyols in general with allyl glycidyl ether;glycerol-1,3-diallyl ether by reaction of equimolar amounts of allylalcohol and allyl glycidyl ether; diallyl alcohols or diols by reactionof allyl chloroformate with diamino alcohols or diols; thioether ortertiary amino group-containing diallyldiols by reaction of two moles ofallyl glycidyl ether with one mole of sodium sulfide or an organicdithiol, or with a primary or di-secondary amine, as is shown in theExamples.

Similarly, the novel R_(F) -acids can be prepared by the reaction of aperfluoroalkyl iodide and an allyloxy acid or its ester, to yield aniodide compound, followed by dehydrohalogenation with a base and, if theproduct is an ester, hydrolysis to the free acid. Useful allyloxy acidscan be prepared advantageously from allyl glycidyl ether and mono- ordiaminoacids, mercaptoacids and hydroxyacids, or from allyl chloride orbromide by reaction with ester-alcohols, followed by hydrolysis of theester group. Also useful is the diallyl-diacid obtained by reaction ofallyl chloride or allyl bromide with ethylenediamine diacetic acid.

Compounds of the formula II can be obtained by the reaction of 2-20moles of allyl glycidyl ether with a compound having 1-4 activehydrogens such as an alcohol, diol, triol, tetraol or a compound of theformula Z(--OH)₁₋₄ ; a thiol, dithiol or a compound of the formulaZ(--SH)₁₋₂ ; a secondary amine, disecondary amine or a compound of theformula Z(--NR₁)₁₋₂, where Z in each case is as defined above, whichproduct is then further reacted with 2-20 moles of a perfluoroalkyliodide in the presence of a free radical initiator to gave an R_(F) I-adduct which is then dehydroiodinated with a base.

Suitable alcohols for preparing compounds of the formula II are thosewith 1 to 20 carbon atoms such as methanol, isopropanol, allyl alcohol,11-undecenol, N,N-dimethylaminoethanol and hydroxybenzoic acid,alkoxylated C₁ -C₂₀ alkanols such as C₁₈ H₃₇ (OCH₂ CH₂)₅₋₅₀ OH andalkoxylated C₁ -C₁₀ alkylphenols such as C₉ H₁₉ C₆ H₄ (OCH₂ CH₂)5--OH.Useful diols include alkylene glycols with 2-6 carbon atoms such asethylene or propylene glycol, 2,2-bishydroxymethylpropionic acid methylester hydroxypropionic acid, N-methyl diethanolamine, allyl glycerol andpolypropylene oxide- or polybutylene oxide-derived diols with 2-20repeating units. Useful triols include trimethylolpropane, glycerine andbutanetriol. Useful tetraols include pentaerythritol and erythritol.Useful thiols include mercaptopropionic acid, thioglycerol, thiophenoland ethylene dimercaptopropionate. Useful amines include butylamine,N,N-dimethylpropane-1,3-diamine, alanine, glutamic acid, aspartic acidand 1,1-dihyroxymethylpropylamine.

The addition and/or oligomerization of allyl glycidyl ether can becarried out under anhydrous conditions using a base such as sodiumhydroxide or an acidic catalyst such as BF₃. Addition reactions of allylglycidyl ether with amines or thiols can be carried out in an aqueousmedium using base catalysis.

The addition of an R_(F) -iodide to an allyl alcohol or acid proceedsreadily in the presence of a free radical initiator such as an azocompound or peroxide at conventional initiation temperatures of 35° to150° C. It was found, however, that only in the presence of smallamounts of aqueous solutions of sulfite, bisulfite or dithionate ionsdoes the reaction proceed fast enough and are conversions high enough tomake the synthesis commercially practical. The novel process to make thecompounds of this invention is described separately in copendingapplication Ser. No. 08/270,068, filed Jul. 1, 1994.

Solvents can be present during the R_(F) -iodide addition reaction; forexample ketones such as acetone, methyl ethyl ketone or methyl propylketone, esters such as isopropyl acetate, alcohols such as ethanol orbutanol, ethers such as dioxane or di(2-hydroxyethyl) ether,hydrocarbons such as toluene or octane, amides such as dimethylformamideand lactams such as N-methylpyrrolidone.

The dehydrohalogenation of the R_(F) -iodide addition product isgenerally carried out in water at 50° to 100° C. by reacting the adductwith a strong inorganic base, such as sodium or potassium hydroxide or astrong organic base such as 1,8-diazabicyclo(5.4.0)-undec-7-ene (DBU)over a period of several hours. The product is obtained in thenon-aqueous phase. The solvent can be stripped off and the product bewashed with water and isolated as a solid by filtration, or it can bedischarged from the reactor as a melt; alternatively, it can be isolatedas a solution by allowing a clean phase separation to occur between theaqueous and organic phases. The mode of isolation will depend on thespecific product. The product is analyzed for its hydroxyl value priorto further reaction. Trans-olefins are formed predominately, with thecis-/trans ratio being determined by NMR.

The alcohols of the formulae I and lI can be further reacted withphosphorous pentoxide, POCl₃ or polyphosphoric acid to make phosphateester-acids, or with chlorosulfonic acid or sulfamic acid to makesulfate ester-acids which are useful as paper sizes. By reactingalcohols of the formula I or II with chloroacetic acid, bromoacetic acidor the like, carboxylic acids can be prepared for use as paper sizes.The alcohols and diols can also be reacted with dicarboxylic acids,dicarboxylic acid anhydrides, tetracarboxylic acid dianhydrides or withdiacid chlorides to prepare carboxylic ester-acids. By reaction withphosgene, dimethylcarbonate or ethylene bischloroformate, carbonates andpolycarbonates can be prepared.

The novel di- and poly-R_(F) -acids of this invention--for examplecompounds of the formula I wherein X is O--CH₂ --COOH or COOH; compoundsobtainable by reacting alcohols of the formulae I and II withdicarboxylic acids, dicarboxylic acid anhydrides, tetracarboxylic aciddianhydrides or with diacid chlorides; sulfates, sulfonates andphosphates of alcohols of the formulae I and II and compounds of theformula II wherein Z is substituted by carboxyl, carboxyalkyl orsulfonate and their salts--are useful as paper sizes which impartoutstanding oil and water repellency. The excellent oil repellancyobtained with these novel compounds is attributed to their bis-R_(F)-structure. As a notable exception, however, it was found that11-perfluoroalkyl-10-undecenoic acid, R_(F) CH═CH--(CH₂)₈ --COOH, and11-perfluoroalkyl-10-undecenyl sulfate, in salt form, performexcellently as an internal paper sizes, perhaps due to their long,linear 2-phase structure. Useful salts are alkali metal, ammonium andamine salts, with ammonium, and mono-, di- and tri-C₁ -C₅ alkyl andmono-, di- and tri-C₁ -C₅ hydroxyalkyl ammonium salts being preferred.Typical salts are those of diethanolamine.

The use of 11-perfluoroalkyl-10-undecenoic acid and of11-perfluoroalkyl-10-undecenyl sulfate as internal oil repellent papersizes is another object of this invention.

Polyurethanes are prepared from the R_(F) -diols of this invention bythe known methods of polyurethane chemistry. These polyurethanes maycontain other building blocks derived from diols or diamines, especiallytertiary amino group-containing diols such as N-methyldiethanolamine,poly(ethylene oxide)diols and 3-aminopropyl-terminated poly(ethyleneoxide) (Jeffamine-ED, from TEXACO Corp.),poly(dimethylsiloxane)dialkanols andpoly(dimethylsiloxane)diaminoalkyls. Typical polyurethane compositionsincorporating these and other diols and aliamines in combination withcertain other perfluoroalkyl-substituted diols are described for examplein U.S. Pat. Nos. 3,968,066, 4,046,944 and 4,098,742. Polyurethanesprepared from the R_(F) -diols of this invention are useful as as oil-and water-repellant coatings on textiles, paper, wood and othersubstrates.

Preferably a sufficient amount of an organofluorine compound of thisinvention is employed to provide 0.01 to 1%, especially 0.03 to 0.2% Fto a substrate.

EXPERIMENTAL PART

The following examples illustrate various embodiments of the invention,and are not to be interpreted as limiting the scope of the appendedclaims. In the examples all pans are by weight unless otherwisespecified.

EXAMPLE 1

1-Butanol,2,2-bis(((4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-undecenyl)oxy)methyl)-.

Into a three neck 250 ml round-bottomed flask are placed 22.7 g (0.042mol) of 1-iodoperfluorooctane, 4.3 g (0.02 mol) of trimethylolpropanediallyl ether (NEOALLYL T-20; 86% by weight diallyl-, 8% monoallyl-, 8%triallyl-substituted, from DAISO Co., Ltd). and 10 g of deionized water.This mixture is placed under nitrogen and heated to 75° C. To the twophase reaction mixture are added 0.22 g (1.37 mmol) of2,2-azo-bis-isobutyronitrile (AIBN) and 0.2 g (0.002 mol) of sodiumbisulfite. After 8 hours the reaction is complete as determined by gaschromatography and the aqueous phase is separated. The reaction mixtureis washed twice with 40 g of deionized water at 75° C.Dehydrohalogenation is performed by the addition of 40 g of deionizedwater and 7.6 g (0.05 mol) of 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU).This mixture is stirred at 80° C. for 5 hours. The aqueous layer isremoved and the reaction mixture is washed with 40 g of deionized water,followed by 40 g of 5% HCl and finally with another 40 g of deionizedwater. The title product is isolated as a tan oil in a yield of 19.4g(72%). MS, m/z (M+); calculated, 1050.0870; observed, 1050.0842. ¹H-NMR (500 MHz, CDCl₃)d6.44(dm, 2H, --CF₂ CH═CH--, J=15.3 Hz), 5.89(dt,2H, --CF₂ CH═CH--, J=15.3 Hz and J=11.9 Hz), 4.14(bs, 4H, --CF₂ CH═CH₂O--), 3.63(s, 2H, --CH₂ OH), 3.52(d, 2H, OCH_(a) H_(b) C--, J_(a),b =9.2Hz), 3.49(d, 2H, --OCH _(a) H_(b) C--, J_(a),b =9.2 Hz), 1.42(q, 2H,--CH₂ CH₃ , J=7.7 Hz) and 0.88(t, 3H, --CH₂ CH₃, J=7.7 Hz). The productcontains 93% of the trans isomer as determined from integration of the ¹H-NMR spectrum.

EXAMPLE 2

1-Propanol,3-((4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-undecenyl)oxy)-2,2-bis(((4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-undecenyl)oxy)methyl).

Into a 100 ml three neck round-bottomed flask are placed 0.64 g (2.5mmol) of the triallyl ether of pentaerythritol (NEOALLYL T-30,containing 15 weight % diallyl, 75% triallyl and 10% tetraallyl esters;DAISO Co., Ltd)., 5.0 g (9.2 mmol) of 1-iodoperfluorooctane and 5.0 g ofdeionized water. The reaction mixture is placed under nitrogen andheated to 80° C. To the stirred reaction mixture are added 0.05 g (0.30mmol) of AIBN and 0.05 g (0.05 mmol) of sodium bisulfite. After 10 hoursthe reaction is complete as determined by gas chromatography. The topwater layer is removed and the reaction mixture is washed twice with 5.0g of deionized water. Dehydrohalogenation is performed by adding 2.0 gof deionized water along with 2.1 g (14.0 m mol) of DBU. This mixture isstirred under nitrogen at 80° C. for one hour, after which time thereaction is complete. The top aqueous layer is removed and the reactionmixture is washed with 2.0 g of deionized water, followed by 2.0 g of 5%HCl and finally with another 2.0 g of deionized water. The title productis isolated as a light brown oil in a yield of 2.1 g (57%). ¹ H-NMR (300MHz, CDCl₃)d6.43(d, 3H, --CF₂ CH═CH--, J=15.5 Hz), 5.88(dt, 3H, --CF₂CH_(a) ═CH_(b) CH₂ c--, J_(a),b =15.0 Hz and J_(a),c =7.5 Hz), 4.13(bs,6H, --CF₂ CH═CH₂ O--), 3.74 (s, 2H, --CH₂ OH) and 3.55 (s, 6H, --OCH₂C--). The product contains 90% of the trans isomer as determined fromintegration of the ¹ H-NMR spectrum. MS, m/z (M⁺); calculated,1511.0704; found, 1511.1586.

EXAMPLE 3

1-Butanol, 2,2-bis(((perfluoroC₆₋₁₈ alkyl-2-propenyl)oxy)methyl)- isprepared from a perfluoroalkyl iodide (TEL-AN, from DuPont) having thefollowing homologue distribution: 1.7% C₆, 49.8% C₈, 33.5% C₁₀, 11.1%C₁₂, 3.1% C₁₄, 0.69% C₁₆ and 0.16% C₁₈.

Into a 1000 ml round-bottomed flask are placed 277 g (0.46 mol)perfluoroalkyl iodide, 50 g (0.23 mol) trimethylolpropane diallyl ether(NEOALLYL T-20; 86% by weight diallyl-, 8% monoallyl-, 8%triallyl-substituted, from DAISO Co., Ltd.), 157 g deionized water and55.2 g (0.69 mol) of 50% sodium hydroxide. The reaction mixture isheated to 85° C. and 1.3 g (0.007 mol) of azo-bis-isobutyronitrile(AIBN) and 0.02 mol) sodium bisulfite are added. This mixture is stirredvigorously under nitrogen. After 24 hours the reaction is complete. Thetop aqueous layer is removed and the reaction mixture is washed with 100g of deionized water followed by 100 g of 5% HCl and finally withanother 100 g of deionized water. The product contains 73% of the transisomer as determined from integration of the ¹ H-NMR spectrum. The ¹H-NMR of the trans isomer is consistent with that obtained from1-butanol,2,2-bis(((4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-undecenyl)oxy)methyl)-,of example 1. ¹ H-NMR, cis isomer: (500 MHz, CDCl₃)d6.23(dm, 2H, --CF₂CH═CH--, J=13.5 Hz), 5.58(dt, 2H, --CF₂ CH═CH--, J=15.6 Hz and J=13.5Hz), 4.27(bs, 4H, --CF₂ CHCH═CH₂ O--), 3.60(s, 2H, --CH₂ OH), 3.48-3.42(4H, --OCH_(a) H_(b) C-- and --OCH_(a) H_(b) Cl13 ), 1.42 (q, 2H, --CH₂CH₃, J=7.0 Hz) and 0.85 (t, 3H, --CH₂ CH₃, J=7.0 Hz).

EXAMPLE 4

1-Propanol, 3-(perfluoroC₆₋₁₈alkyl-2-propenyl)oxy)-2,2-bis-((perfluoroC₆₋₁₈-alkyl-2-propenyl)oxy)methyl)-, is prepared from a perfluoroalkyl iodideTEL-AN, from DuPont) having the following homologue distribution: 1.7%C₆, 49.8% C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69% C₁₆ and 0.16% C₁₈.

Into a 2000 ml glass reactor are charged 1394 g (2.32 mol)perfluoroalkyl iodide, 200 g (0.78 mol) of triallyl ether ofpentaerytrerythritol (NEOALLYL T-30, containing 15 weight % diallyl, 75%triallyl and 10% tetraallyl esters; DAISO Co., Ltd.), 2.7 g (0.014 mol)azo-bis-isobutyronitrile (AIBN) and 1.2 g (0.116 mol) sodium bisulfite,538 g deionized water and 311 g (3.89 mol) 50% NaOH. The temperature ofthe mixture is increased to 85° C. and it is stirred vigorously. After 6hours a second charge of 1.8 g (0.009 mol) of AIBN is made. After 18hours the reaction is complete and the top aqueous layer is removed. Thereaction mixture is washed with 269 g deionized water at 85° C.,followed by a wash with 107.6 g of 5% HCl and a final wash with 269 gdeionized water at 85 ° C. The product is isolated as a waxy yellow towhite solid in a yield of 1249 g (95%), m.p. 72°-80° C. The productcontains 73% of the trans isomer as determined from integration of the ¹H-NMR spectrum. The ¹ H-NMR of the trans isomer is consistent with thatobtained from 1-propanol,3-((4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-undecenyl)oxy)-2,2-bis(((4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-2-undecenyl)oxy)methyl)-,of example 2. ¹ H-NMR, cis isomer (500 MHz, CDCl₃) d6.22(bm, 3H, --CF₂CH═CH--), 5.62 (dt, 3H, --CF₂ CH_(a) ═CH_(b) CH₂ c--, J_(a),b =13.7 Hzand J_(a),c =15.4 Hz), 4.28(bs, 6--CF₂ CH═CH₂ O--), 3.72(s, 2H, --CH₂OH) and 3.53 (s, 6H, --OCH₂ C--).

EXAMPLE 5

1-Propyldihydrogenphosphate, 3-(perfluoro-C₆₋₁₈alkyl-2-propenyl)oxy)-2,2-bis-(perfluoro-C₆ -C₁₈alkyl-2-propenyl)oxy)methyl)-.

Into a 500 ml three neck round-bottomed flask are placed 100 g (0.061mol) of 1-propanol, 3-(perfluoro-C₆₋₁₈alkyl-2-propenyl)oxy)-2,2-bis((perfluoro-C₆₋₁₈alkyl-2-propenyl)(oxy)methyl)-, as prepared in Example 4, along with 144g of glyme. The temperature of this solution is increased to reflux (85°C.) and 28 g of glyme is removed by distillation. To this stirredsolution is added 35.8 g (0.12 mol) of polyphosphoric acid undernitrogen. This mixture is stirred vigorously for 12 hours. After 12hours the reaction mixture is poured into 1000 g of deionized water anda tan colored precipitate is formed. The precipitate is isolated on aBuchner funnel to give 103 g (98% yield) of the title compound, m.p.50°-58° C.

A CDCl₃ solution of the product is acidified with TFA-d7 and derivatizedwith BSTFA. The ³¹ P-NMR (500 MHz, CDCl₃), complex signals at d-18 ppmare consistent with the bistrimethylsilyl ester of1-propyldihydrogenphosphate, 3-(perfluoro-C₆₋₁₈alkyl)-oxy)-2,2-bis((perfluoro-C₆₋₁₉ alkyl)oxy)methyl)-, being the majorproduct. Other signals at -26.4 ppm and -32 ppm are consistent withinorganic phosphorous and pyrophosphate type phosphorous respectively.Signals at -22.6 ppm and -31.3 ppm are consistent with a dimer typestructure.

EXAMPLE 6

2-Propanol, 1,3-bis((perfluoro-C₆₋₁₈ alkyl-2-propenyl)oxy)-, is preparedusing the following homologue distribution of perfluoroalkyl iodide:1.7% C₆, 49.8% C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69% C₁₆ and 0.16%C₁₈ (TEL-AN, from DuPont).

Into a 1000 ml three neck round-bottomed flask are placed 53.0 g (0.31mol) 1,3-diallyl ether of glycerol, 373 g (0.62 mol) perfluoroalkyliodide, 21 g deionized water and 74.4 g (0.93 mol) 50% sodium hydroxide.The reaction mixture is placed under nitrogen and the temperature isincreased to 85° C. with stirring. 1.79 g (0.93 m mol)azo-bis-isobutyronitrile are added. After 12 hours the reaction iscomplete. The reaction mixture is washed with 300 g deionized water at85° C., followed by a wash with 150 g of 5% HCl and a final wash with300 g deionized water at 85° C. The product is isolated as a waxy brownsolid in a yield of 283 g (82%), m.p. 37°-45° C. The product contains64% of the trans isomer as determined from integration of the ¹ H-NMRspectrum. ¹ H-NMR, trans isomer (500 MHz, CDCl₃) d6.45 (dm, 2H, --CF₂CH═CH--, J=14.6), 5.93 (dr, 2H, --CF₂ CH_(a),═CH_(b) CH₂ c--, J_(a),b=14.6 Hz and J_(a),c =11.0 Hz), 4.19(bs, 4H, --CH═CHCH₂ O--),4.02(quintet, 1H, (--CH₂)₂ CHOH, J=5.2 Hz), 3.58 (m, 4H, (--CH₂₂ CHOH).Addition of trichloroacetyl isocyanate resulted in a downfield shift ofthe methene proton from 4.02 to 5.23 ppm. ¹ H-NMR, cis isomer (500 MHz,CDCl₃) d6.27(dm, 2H, --CF₂ CH═CH--, J=12.8), 5.62 (dt, 2H, --CF₂ CH_(a)═CH_(b) CH₂ c--, J_(a),b =12.8 Hz and J_(a),c =14.6 Hz), 4.34 (bs, 4H),--CH═CHCH₂ O--), 3.99 (quintet, 1H, (--CH₂)₂ CHOH, J=5.2 Hz), 3.58 (m,4H, (--CH₂)₂ CHOH).

EXAMPLE 7

2-Propyldihydrogenphosphate, 1,3-bis((perfluoro-C₆₋₁₈alkyl-2-propenyl)oxy)-.

Into a 1000 ml three neck round-bottomed flask are placed 100 g (0.089mol) of 2-propanol, 1,3-bis((perfluoro-C₆₋₁₈ alkyl-2-propenyl)oxy)-,along with 150 g of glyme. The temperature of this solution is increasedto reflux (85° C.) and 15 g glyme is removed by distillation. Removal ofglyme is used as a drying procedure. To this refluxing solution is added107.3 g (0.36 mol) of polyphosphoric acid under nitrogen. This mixtureis stirred vigorously for 18 hours. After 18 hours the reaction mixtureis poured into 1000 g of deionized water with stirring and a browncolored precipitate forms. The precipitate is isolated on a Buchnerfunnel and dried under vacuum to give 94 g (88% yield), m.p. 60°-65° C.

A CDCl₃ solution of the product is acidified with TFA-d7 and derivatizedwith BSTFA. ³¹ P-NMR (500 MHz, CDCl₃), shows a set of two doublets at-17.95 with J=9 Hz. These signals are consistent with thebistrimethylsilyl ester of cis/trans 2-propanol, 1,3-bis((perfluoroC₆₋₁₈alkyl-2-propenyl)oxy)-.

EXAMPLE 8

Reaction of 1-Propanol, 3-((perfluoroC₆₋₁₈alkyl-2-propenyl)oxy)-2,2-bis((perfluoroC₆₋₁₈alkyl-2-propenyl)oxy)methyl)-, with hexamethylene diisocyanate.

Into a flame dried 100 ml three neck round-bottomed flask are placed20.0 g (0.012 mol) of 1-propanol, 3-(perfluoroC₆₋₁₈alkyl)oxy)-2,2-bis((perfluoroC₆₋₁₈ alkyl)oxy)methyl)- along with 42 gisopropyl acetate. This solution is heated to reflux (85° C.) withstirring and 8 g isopropyl acetate is removed by distillation. To thissolution is added 20 mg (0.07 m mol) of stannous octoate and 1.0 g(0.006 mol) of hexamethylene diisocyanate (HMDI). The reaction mixtureturns white immediately after the addition of HMDI. Progress of thereaction is monitored by following the disappearance of the isocyanatefunctionality in the infrared spectrum. Isopropyl acetate is removedunder vacuum to give a brown solid in a yield of 16.8 g (80%). An IRspectrum of a thin film shows an n_(max) at 1715.9 cm⁻¹ (--O--C(O)NH--).

EXAMPLE 9

Poly-(((3-perfluoroalkyl-2-propenyl)oxy)methyl)-oxirane).

A) Synthesis of HO--(--CH₂ CH(--CH₂ --O--CH₂ CH═CH₂)_(n))--OH.

Into a 1000 ml three neck flask equipped with a condenser, stirringshaft, thermometer and dropping funnel fitted with a gas inlet tube areadded 62.1 g (1.0 mol) ethylene glycol and 2.3 g boron trifluorideetherate. 399.6 g (3.5 mol) allyl glycidyl ether is charged to thedropping funnel and dripped into the reaction vessel while stirring andintroducing a stream of nitrogen gas over a period of 6 hours. The rateof addition is controlled to maintain the exotherm temperature between70° and 80° C. After the addition is complete, the reaction mixture isheated at 80° C. for 3.5 hours. At that time a small sample is removedand analyzed using a VG Auto Spec Q hybrid mass spectrometer with LiquidSIMS technique.

The analysis shows that the oligomeric product has a chain lengthdistribution as shown (n=number of repeat units):

    ______________________________________                                        n     1     2   3   4    5    6    7    8    9    10                          ______________________________________                                        % by  5.0   7.7 18.6                                                                              22.6 21.5 14.2 7.2  2.0  0.9  0.2                         weight                                                                        ______________________________________                                    

B ) Synthesis of HO--(--CH₂ CH(--CH₂ --O--CH₂ CH═CH₂ --R_(F))O_(n))--OH.

To a one-liter 3-neck flask equipped with a condenser, stirring shaftand gas inlet are charged 55.2 g (0.12 mol) of the aboveallylether-substituted oligooxyethylene mixture, (250.0 g, 0.42 mol)perfluoroalkyl iodide with a homologue distribution of 1.7% C₆, 49.8%C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69% C₁₆ and 0.16% C₁₈ (TEL-AN,from DuPont), 125.0 g water, 2.0 g 2,2'-azo-bis-(2-methylbutyronitrile)and 0.6 g (0.006 mol) sodium bisulfite. The resultant reaction mixtureis heated to 80° C. and held at this temperature for 6 hours withstirring and introducing a stream of nitrogen gas. At this time, gaschromatography shows that the starting perfluoroalkyl iodide isconsumed. The product is washed two times with water (˜150 g per wash).To the resultant orange semi-solid is added sodium hydroxide (50%, 37.6g, 0.47 mol) and 120.0 g H₂ O. This mixture is heated at 80° C. withstirring for 16 hours, followed by neutralization with 10% hydrochloricacid and two water washes (˜120 g per wash). To remove any residualwater, the product is azeotroped with toluene. The toluene is vacuumdistilled, yielding a tan waxy solid.

By NCO titration, the hydroxy value is found to be 1353 (theoretical,1060). Fluorine analysis shows the product to be 55% F, 92% of theory.

EXAMPLE 10

Synthesis of 2-propylsulfate, 1,3-bis((perfluoro-C₆₋₁₈alkyl-2-propenyl)oxy)-, ammonium salt.

Into a 50 ml three neck round-bottomed flask is placed 15 g (0.014 mol)of 2-propanol, 1,3-bis((perfluoroC₆₋₁₈ alkyl-2-propenyl)oxy)-, alongwith 5.3 g (0.055 m mol) of sulfamic acid and 1.4 g (0.0166 mol)pyridine. It is then heated at 100° C. for 6 hours. The final product isa brown, hard solid containing 44.3% F.

¹ H-NMR (500 MHz, CDCl₃)d3.8 (CHOCH₂,4 Hm), 4.2 (OCH₂ CH,4Hdd), 4.7(OCHCH₂,quin), 5.9 (CH₂ CCH═,2H,dd), 6.4 (R_(F) CH,2H,m).

EXAMPLES 11-13

Using the methods described in Examples 1-9, the following additionalperfluoroalcohols are prepared:

    ______________________________________                                        Example                                                                              Perfluoroalkyl-alcohol                                                 ______________________________________                                        11     (C.sub.6 F.sub.13 CH═CHCH.sub.2 OCH.sub.2).sub.n --C(CH.sub.2             OH).sub.4-n n = 2, 3                                                   12     (C.sub.6 F.sub.13 CH═CHCH.sub.2 OCH.sub.2).sub.2 C(C.sub.2                H.sub.5)CH.sub.2 OH                                                    13     (C.sub.8 F.sub.17 CH═CHCH.sub.2 OCH.sub.2).sub.2 CHOH.             ______________________________________                                    

EXAMPLE 14

Synthesis of a di-(2-hydroxy-4-oxa-6,7-ene-7-perfluoroalkyl)-thioether.

A 150 ml three-necked, round-bottomed flask is charged with 19.2 g (0.08mol, 98%) sodium sulfide nonahydrate and 60 g deionized water. Thesolution is heated to 42° C. and 18.2 g (0.16 mol) allyl glycidyl etheris added over a one hour period to give a cloudy solution. The reactionmixture is heated at 60° C. for one hour. The product mixture isconcentrated on a rotary evaporator with reduced pressure at 70° C. togive a slightly viscous, clear, brown oil in 88% yield (18.3 g).Analytical data: ¹ H NMR (500 MHz, CDCl₃) d: 2.50-2.70 (4H, m, --CH₂S--), 3.71 and 3.72 (8H, M --OCH₂ CHOH-- and CH₂ ═CHCH₂ --) 3.87 (2H, m,--CH₂ CHOHCH₂ O, 5.00 and 5.14 (4H, dd, CH₂ ═CH--), 5.80 (2H, m, CH₂═CHCH₂).

8.4 g (0.032 mol) of this thio ether secondary diol, 38.0 g (0.063 mol)perfluoroalkyl iodide with a homologue distribution of 1.7% C₆, 49.8%C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69% C₁₆ and 0.16% C₁₈ (TEL-AN,from Du Pont), 0.3 g (1.90mmol) AIBN, and 1.2 g (0.006 mol) sodiummetabisulfite is stirred under nitrogen gas at 70° C. in a three-necked,round-bottomed flask. After 1.5 hours, the reaction is complete based ongas chromatography.

Dehydrohalogenation is performed by the addition of 25.2 g (0.32 mol,50%) sodium hydroxide. The mixture is stirred at 90° C. for 20 minutesto allow for completion. The aqueous layer is removed and the organiclayer is taken up in 150 ml 2-pentanone. After 2 successive washes with100 ml deionized water each, the solvent is stripped off on a rotaryevaporator under reduced pressure to give a yellow solid in a yield of32.0 g (83.4%). ¹ H NMR (500 MHz, CDCl₃) d: 2.7 and 2.8 (4H, m, --CH₂S--), 3.5 (4H, m,--OCH₂ CHOH--, 3.95 (2H, m, --CH₂ CHOHCH₂ --), 4.2 and4.35 (4H, m, --CH₂ CH₂ O--, cis/trans coupling with olefinic hydrogens),5.6 and 5.9 (2H, m, CF₂ CH--CH--), 6.3 and 6.45 (2H, m,--CH═CH═CH₂ --).The product contains 71% trans isomer as determined from integration.

EXAMPLE 15

Synthesis of a di-(2-hydroxy-4-oxa-6,7-ene-7-perfluoroalkyl)-butylamine.

Distilled n-butylamine (10.0 g, 0.137 mol) is dissolved in 30 gdeionized water in a three-necked, 250 ml round-bottomed flask. Thesolution is heated to 40° C. and 31.3 g (0.274 mol) allyl glycidyl etheris charged over 30 minutes; the temperature of the mixture spontaneouslyrises to 60° C. and is maintained there for 6 hours. After this time theproduct is concentrated at reduced pressure on a rotary evaporator togive a clear, yellow liquid in 98% yield (40.4 g). Analytical data: ¹ HNMR (500 MHz, CDCl₃) d: 5.8 (2H, m, CH₂ ═CH--), 5.2 (2H, dd, CH₂ ═CH--,trans), 5.1 (2H, dd, CH═CH--, cis), 3.9 (4H, t, --CHCH₂ O--), 3.8 (2H,bs,--CH₂ CHOHCH₂ --), 3.4 (4H, m, --OCH₂ CHOH--), 2.5(4H, m, --CHOHCH₂N-- and 2H, m, --NCH₂ CH₂), 1.4(2H, quintet, --CH₂ CH₂ CH₂), 1.2 (2H,sextet, --CH₂ CH₂ CH₃), 0.8 (3H, t, --CH₂ CH₃).

11.7 g (0.039 mol) of the above diallyloxy-butylamine diol, 47.0 g(0.078 mol) perfluoroalkyl iodide with a homologue distribution of 1.7%C₆, 49.8% C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69% C₁₆ and 0.16% C₁₈,1.5 g (0.008 mol) sodium metabisulfite, and 14 g deionized water arecharged into a 250 ml three-necked, round-bottomed flask. Undernitrogen, the biphasic mixture is heated to 70° C. and a charge of 0.63g (3.92 mmol) azo-bisisobutyronitrile (AIBN) is made. A temperature riseof 11° C. is noted. Once cooled back to 70° C., the reaction mixture isallowed to go to completion. This takes 1.5 hours as determined by gaschromatography.

Dehydrohalogenation is carried out by the addition of 12.8 g (0.16 mol,50%) sodium hydroxide. The mixture is stirred at 90° C. for 3 hours. Theaqueous layer is removed and the organic layer is washed three timeswith 200 ml slightly alkaline, deionized, water. The final product isisolated as a brown, thick syrup in 88.6 % yield (43.2 g). Analyticaldata: ¹ H NMR (500 MHz, CDCl₃) d: 6.5 (2H, d, --CF₂ CH₂ ═CH-transcoupling), 6.3 (2H, m, --CF₂ CH═CH--, cis coupling), 5.9 (2H, m, CF₂CH═CH--, trans coupling), 5.6 (2H, m, --CF₂ CH═CH--, cis coupling), 4.1(4H, bs, --CH═CH--CH₂), 3.9 (2H, m, --CH₂ CHOHCH₂ --), 3.5 (4H, m,--OCH₂ CHOH--), 2.6 (4H, m, --CHOHCH₂ N-- and 2H, t, --CH₂ CH₂ N--), 1.4(2H, quintet, --CH₂ CH₂ CH₂ --), 1.3 (2H, sextuplet, --CH₂ CH₂ CH₃), 0.9(3H,t, --CH₂ CH₃). The product contains 72% trans isomer as determinedfrom integration.

EXAMPLE 16

Synthesis of a di-R_(F) -diacid: preparation of R_(F) -allyl glycidylether adduct with ethylenediamine diacetic acid.

51.45 g (0.0850 moles) R_(F) -iodide with a chain length distribution asin Example 3 (TEL AN, from DuPont), 15.0 g water and 10.00 g (0.0850moles) allyl glycidyl ether are weighed into a 250 ml 3-neckround-bottomed flask equipped with a mechanical stirrer, nitrogen inlet,thermometer and condenser. The reaction mixture is heated to 80° C.while stirring and 0.33 g (0.0017 moles)2,2'-azo-bis-(2-methylbutyronitrile) (VAZO-67, from WAKO Chem. Co.) areadded. An additional 0.16 g (0.00083 moles) VAZO 67 are added after twohours and another 0.48 g (0.0025 moles) of VAZO 67 after four hours. Thereaction is continued for five hours at 65° C. A subsequent GC scanshows only a minute amount of R_(F) -iodide remaining. To this mixtureare added 55.42 g (0.0425 moles) commercial ethylenediamine diaceticacid sodium salt solution (16.88% actives by amine titration) and 2 g50% NaOH. The reaction temperature is raised to 90° C. and the mixtureis stirred for 5 hours. 5 g 50% NaOH and 10 g 1-propanol are added andthe reaction mass is kept at 93° C. for 10 hours. To effectdehydrohalogenation, 15 ml 50% NaOH are added and the reaction mixtureis stirred at 93° C. for 14 hours. The mixture is transferred to a 1000ml Erlenmeyer flask and 500 g water and enough acetic acid are added toreduce the pH to 3; then the mixture is cooled with an ice bath. Theprecipitate is filtered off and dried under vacuum. Yield is 71% (byweight). Elemental analysis: 29.9% C, 2.0% H and 1.6% N (theoretical:32.1 C%, 2.21% H and 2.06% N).

For application testing the acid is neutralized with NaOH and dissolvedin water.

EXAMPLE 17

The following examples describe the synthesis of polyurethanes.

40.17 g (31.4 mmoles) of the diol of example 14 and 86.27 g isopropylacetate are placed in a 250 ml 3-necked round-bottom flask fined with amechanical stirrer, gas inlet, thermometer, Dean-Stark trap andcondenser. The system is kept under nitrogen and heated to reflux toremove water as an azeotrope with isopropyl acetate: 18 ml of distillateare collected in the trap. The contents are cooled to 75° C. and 5.03 g(23.6 mmoles) of 2,2,4-trimethyl-1,6-diisocyanatohexane (TMDI) are addedfollowed by 0.10 g (0.16 mmoles) dibutyltin dilaurate (DBTL). Thecontents are stirred at 80° C. until the TMDI content is 0.5% asdetermined by IR (6 hrs). 11.57 g (19.5 mmoles) of Dimer AcidDiisocyanate (DDI 1410, (from Henkel Chemie) and 1.45 g (12.2 mmoles)ofN-methyl diethanolamine (NMDEA) are added, followed by 16.3 g isopropylacetate as a rinse. The mixture is stirred for 6 hours at 80° C. Afterthis time no more NCO groups remain present as determined byIR-spectroscopy. The product polyurethane is obtained as a 40% solutionin isopropyl acetate and contains the diol of Ex. 14, TMDI, DDI, andNMDEA in a mol ratio of 4:3:2.5:1.5. On drying the polyurethane forms atough clear film.

EXAMPLES 18 and 19

Following the procedure of Example 17, polyurethanes are prepared fromthe R_(F) -diols of Examples 14 and 15; their compositions andproperties are listed in the table below.

EXAMPLE 20

Synthesis of a polyurethane from the allylether-substitutedoligo-ethyleneoxide diol of Example 9.

In a 250 ml 3-necked round-bottomed flask fined with a mechanicalstirrer, gas inlet, thermometer, Dean-Stark trap and condenser areplaced 40.29 g (25.5 mmoles) of the oligoether diol of Example 9 and118.37 g isopropyl acetate. The system is kept under nitrogen and heatedto reflux to remove water as an azeotrope with isopropyl acetate: 18.3ml of distillate are collected in the trap. The contents are cooled to75° C., and 24.34 g (41.1 mmoles) of Dimer Acid Diisocyanate (DDI 1410,(from Henkel Chemie) are added followed by 0.10 g (0.16mmoles)dibutyltin dilaurate (DBTL) and 1.65 g (13.8 mmoles) ofN-methyl-diethanolamine (NMDEA). The contents of the flask are heated to80° C. and stirred for 5 hours, after which time no NCO groups arepresent as determined by IR-spectroscopy. The product polyurethane isobtained as a 40% solution in isopropyl acetate. It contains the diol ofExample 2, DDI, and NMDEA in a tool ratio of 1:1.5:0.5.

EXAMPLE 21a-d

The polyurethane solutions were diluted with isopropyl acetate to 1%solids and coated onto glass microscope slides, which were air dried andheated for ten minutes at 60° C. before measuring contact angles ofwater and decane. The results show that the coatings are both water- andoil-repellent.

    ______________________________________                                        EX.  diol of Composition, mol ratio of                                                                         Contact angles                               21-  EX.     R.sub.F -diol/TMDI/DDI/NMDEA                                                                      water decane                                 ______________________________________                                        a    14      4:3:2.5:1.5         106   66                                     b    15      4:3:2.5:1.5         104   49                                     c     9      4:3:2.5:1.5         108   61                                     d    15      1:0:1.5:0.5         110   65                                     ______________________________________                                    

EXAMPLE 22

This example illustrates the synthesis of a di-perfluoroalkylsulfateester ammonium salt by reaction with sulfamic acid.

Into a 100 ml round-bottomed flask are placed 1-propanol,3-(perfluoroC₆₋₁₈ alkyl-2-propenyl)oxy)-2,2-bis-((perfluoroC₆₋₁₈alkyl-2-propenyl)oxy)methyl)- (from Example 4), (16.46 g, 0.01 mol),sulfamic acid (1.78 g, 0.018 mol) and 3.33 g tetramethylurea. Thismixture is stirred under nitrogen for 1.5 hours at 103° C. Progress ofthe reaction and the final degree of sulfation are monitored by atwo-phase titration of the formed bisperfluoroalkylsulfate ammonium saltwith benzothonium chloride solution according to the procedure describedin, "Analysis of Surfactants", Surfactant Sci. Series, Vol. 40, (MarcelDekker, Inc., New York, 1992).

The final degree of sulfation, expressed as OH equiv. initial --OHequiv. final, is 0.9.

The product is dissolved in water and used for application tests.

EXAMPLES 23-25

Following the procedure of Example 22, the R_(F) -alcohols of Examples 3and 6, and the R_(F) -diol of Example 9 are reacted with sulfamic acid,with the degrees of sulfation indicated:

    ______________________________________                                                      R.sub.F -compound                                                                        Degree of                                            Example No.   of Ex. No. Sulfation                                            ______________________________________                                        22            4          0.9                                                  23            3          0.95                                                 24            6          0.85                                                 25            9          1.0                                                  ______________________________________                                    

EXAMPLE 26

The following example shows the performance of the novel sulfate acidsand carboxylic acid salts, as well as of 11-perfluoroalkyl-10-undecenoicacid salts as internal and external paper sizes.

SAMPLE PREPARATION AND TESTING:

The required amounts of 2% solutions of the test compounds in distilledwater are dissolved in enough aqueous ammonia to achieve completeneutralization of the acid groups; the pH of the resulting solutions ordispersions is 9 to 9.5. Samples of the fluorochemicals are then dilutedto the test application levels with distilled water.

1. External Size Application:

The neutralized test solutions are added to a 4% aqueous solution ofpaper maker's starch (Stayco M, oxidized starch, from Staley Corp.) andthen applied to unsized paper by padding (paper dipped through starchsolution, and passed through single nip rollers). The resulting sheetsare dried at ambient conditions for 15 minutes, then 3 minutes at 200°F. in an "Emerson Speed Drier" (heated metal plate with canvas cover).

Oil Kit Test:

The oil repellency of the surface is determined by using the TAPPI UM557 OIL KIT TEST, which consists of determining with which of twelvecastor oil-heptane-toluene mixtures having decreasing surface tensionpenetration occurs within 15 seconds; ratings go from 1, lowest, to 12.

Grease Resistance Test:

Grease resistance is determined with the Ralston-Purina test for petfood materials; RP-2 Test, Ralston-Purina Company, Packaging ReferenceManual Volume 06--Test Methods.

In summary: cross-wise creased test papers are placed over a grid sheetimprinted with 100 squares. Five grams of sand are placed in the centerof the crease. A mixture of synthetic oil and a dye for visualization ispipetted onto the sand and the samples are maintained at 60° C. for 24hours. Ratings are determined by the percentage of stained gridsegments, using at least two samples.

2. Internal Size Application and Testing:

Six grams of dry recycled pulp consisting of 70% hard-wood and 30%soft-wood are diluted in 289 ml distilled water and thoroughly dispersedin a blender. To this pulp slurry is added the required amount of a 1%solution of the test compound in distilled water and mixed in for 5minutes. Then 6 ml of a 1% aqueous solution of cooked cationic starchare added and mixed together for an additional 5 minutes. To thismixture 24 ml of a 50% (on solids) dilution of a water-repellentadjuvant (Hercon-76, from Nalco Chem. Corp.) are added and mixed in foranother 10 minutes. The resulting slurry is diluted with an additional500 ml of distilled water and mixed again. This mixture is then pouredover a 100 mesh wire screen, with a vacuum applied from below whichpulls the water from the pulp mixture to form a sheet on the screen. Thewet sheet is removed from the screen and dried between another screenand hard surface at a pressure of approximately 0.4 lb./in² at 110° C.for 11/2 hours.

Hot-Oil Test:

One ml of hot (110° C.) corn oil is placed on the paper and the time isrecorded for penetration to occur (20 minutes maximum). Paper made inthe same manner, including the cationic starch and water-repellentadjuvant, but without a fluorochemical, demonstrates an oil kit numberof <1 and holds the hot corn oil for less than one minute (begins topenetrate as soon as applied). The amount of oil absorbed is determinedgravimetrically by weighing the paper before and after the hot-oil test,and after the surface oil has been removed.

The Oil-Kit Test is the same as that for the External Size.

Hot-Water Test:

One ml of a hot (83° C.) 5% lactic acid solution is placed on the paperplate, and hold-out time and absorption are measured the same way as inthe hot-oil test.

The test results are shown in the following table.

    __________________________________________________________________________                       Internal Size                                              R.sub.F -salt of                                                                       External Size  HOLD OUT                                                                             % OIL                                          Ex. No.                                                                             % F                                                                              OIL KIT                                                                            RP-2 OIL KIT                                                                            TIME (MIN)                                                                           ABSORBED                                       __________________________________________________________________________    24    0.05                                                                             0    2 × 100                                                                      2    <1     94                                                   0.07                                                                             0    2 × 100                                                                      2    <1     93                                                   0.1                                                                              4    5, 5 3    >20    30                                             23    0.05                                                                             3    2 × 0                                                                        2    >20    7                                                    0.07                                                                             5    2 × 0                                                                        4    >20    5                                                    0.1                                                                              7    2 × 0                                                                        5    >20    2                                              22    0.05                                                                             4    2 × 0                                                                        2    >20    7                                                    0.07                                                                             5    2 × 0                                                                        4    >20    0                                                    0.1                                                                              6-7  2 × 0                                                                        5    >20    0                                              25    0.05                                                                             5    2, 40                                                                              6    >20    3                                                    0.07                                                                             7    2 × 0                                                                        8    >20    6                                                    0.1                                                                              10   2 × 0                                                                        10   >20    5                                              16    0.05         2    1      100                                                  0.07         4    20     2                                                    0.1          5    >20    3                                              __________________________________________________________________________

EXAMPLE 27

Synthesis ofN,N-(2-hydroxy-4-oxa-7-perfluoroalkyl-6,7-heptenyl)-aspartic acid. a)Synthesis of a diallyl-diacid from aspartic acid and allyl glycidylether.

A mixture of 29.3 g (0.22 mol) aspartic acid, 35.2 g (0.44 mol, 50%)sodium hydroxide, 35 g deionized water, and 30 g n-propanol is stirredat 50°-55° C. in a three-necked, round-bottomed flask equipped withcondenser, dropping funnel and stirrer, 50.2 g (0.44 mol) allyl glycidylether are added over 50 minutes to give a cloudy, biphasic system whichafter an additional hour at 50° C. becomes clear and homogeneous. Thereaction mixture is then stirred for an additional 4 hours at 50°-55° C.Complete consumption of the epoxide is ascertained by gaschromatography.

b) Addition of R_(F) -iodide:

At 30° C., 265 g (0.44 mol) perfluoroalkyl iodide with a homologuedistribution of 1.7% C₆, 49.8% C₈, 33.5% C₁₂, 11.1% C₁₂, 3.1% C₁₄, 0.69%C₁₆ and 0.16% C₁₈ (TEL-AN, from DuPont), 1.7 g (0.0088 mol) VAZO-67, and4.2 (0.022 mol) sodium metabisulfite are charged to the above mixtureunder a nitrogen purge. The slightly yellow, milky mixture is thenheated to 75° C.; the temperature rises to 88° C. After cooling back to75° C., the white, pasty mixture is stirred for an additional 260minutes. At this time the R_(F) I is completely consumed. A charge of36.5 g (0.46 mol, 50%) sodium hydroxide is slowly added to the mixtureto eliminate HI. After 40 minutes the product mixture is cooled to roomtemperature and poured into 3000 ml cold, deionized water. The mixtureis neutralized with dilute HCl to pH 2-2.5, filtered and washed. Dryingis carried out using 25 mm Hg vacuum at 50° C. for 2 days to yield 270 g(94% yield) of off-white powder.

EXAMPLE 28

1 ). Synthesis ofN,N-(2-hydroxy-4-oxa-7-perfluoroalkyl-6,7-heptenyl)-1,1-dihydroxymethylaminopropane.

a) Allyl glycidyl ether addition to amine:

A solution of 42.0 g (0.35 mol) 2-amino-2-ethylpropanediol and 39.7 gdistilled water is stirred at 25° C. in a three-necked, round-bottomedflask equipped with a condenser, dropping funnel and stirrer. 83.2 g(0.73 mol) allyl glycidyl ether are added over 60 minutes to give aclear solution. An additional 1.4 g (0.01 mol)2-amino-2-ethylpropanediol are added and the clear solution is stirred 4hours at 25° C., followed by one hour at 80° C. Complete consumption ofthe epoxide is ascertained by gas chromatography.

b) R_(F) -I addition:

At 25° C., 101.4 g (0.17 mol) perfluoroalkyl iodide with a homologuedistribution of 1.7% C₆, 49.8% C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69%C₁₆ and 0.16% C₁₈ (TEL-AN, from DuPont), 3.2 g (0.02 mol) sodiummetabisulfite and 39.5 g distilled water are charged to a three-necked,round bottomed flask equipped with a condenser and stirrer under anitrogen purge. The slightly yellow mixture is then heated to 85° C. and49.1 g (0.9 mol) of the above solution together with 0.715 g (0.004 mol)Vazo 67 are added. The mixture is stirred at 85° C. for 4 hours. At thistime R_(F) I is completely consumed. A charge of 4.35 g (0.11 mol)sodium hydroxide dissolved in 9.1 g distilled water is slowly made over15 minutes to eliminate HI. After 6.5 hours at 85° C., 30.5 g distilledwater and 5.5 g isopropanol are added. The contents form two layers whenagitation is stopped. The bottom organic layer is washed twice with 25ml hot water; then dried under 25 inches Hg vacuum at 70° C. for 7 hoursto yield 51.0 g (45.5%) of a brown solid.

2). Phosphation:

At 25° C., 12.04 g (0.001 mol) of the amine tetrol of part 2.), 5.99 gpolyphosphoric acid and 4.17 g glyme are charged to a three-necked,round bottomed flask equipped with a condenser and stirrer and using anitrogen purge. The mixture is then heated to 90° C. for 3.5 hours togive a brown viscous mixture. Then 20 g methyl propyl ketone, 20 gdistilled water and 13 g conc. HCl are added and the mixture is stirreduntil it is homogeneous at room temperature. Then the stirrer is stoppedand the contents are allowed to settle out into three layers. The majorcomponent is contained in the middle layer, which is separated andfiltered. A brown paste is obtained, which is dried under 25 inches Hgvacuum at 100° C. for 7 hours to yield a brown solid in 95% yield.

EXAMPLE 29

45.74 g (0.0756 moles) R_(F) -iodide with a R_(F) -chain lengthdistribution of 1.7% C₆, 49.8% C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69%C₁₆ and0.16% C₁₈, (TEL-AN, from DuPont, 23.23g distilled water, 0.75 g(0.004 moles) sodium metabisulfite and 15.27 g (0.083 moles)10-undecylenic acid (C₁₁ -A) are placed in a 100 mol 3-necked roundbottom flask equipped with stirrer, condenser, gas inlet tube andthermometer. The mol ratio of R_(F) -I/C₁₁ -acid is 1/1.09. The mixtureis stirred and sparged with nitrogen and 1 g dry ice, then heated to 80°C. Next 0.0239 g (0.13 mmoles) 2,2'-azobis-(2-methylbutyronitrile) (VAZO67) are added, followed by 0.026 g VAZO-67 after 3 hours and 0.033 gVAZO 67 after 7 hours. The progress of the reaction is monitored byobserving the disappearance of R_(F) I by gas chromatography.

After 9 hours reaction time, 20.0 g of a 50% NaOH solution are added.The mixture is stirred at 70° C. for 3 hours; then is cooled to roomtemperature. The mixture is slowly poured into 1 liter of ice wateracidified with 100 g of a 10% hydrochloric acid solution. Theprecipitate is filtered, washed several times with cold water and driedin vacuo to a tan, waxy solid with a melting point of 43°-54° C. Theyield is 48 g (93% of theory).

EXAMPLE 30

The products of examples 27-30 are dispersed in water and the pH of thedispersions are adjusted to 9; the resulting solutions and dispersionsare used as internal and external paper sizes and the samples are testedas previously described. The following table shows the test results.

    __________________________________________________________________________                     Internal Size                                                                 OIL TEST     WATER TEST                                               External Size                                                                            OIL       WATER                                                    OIL TEST   HOLD      HOLD %                                          Product of                                                                             OIL     OIL                                                                              OUT % OIL OUT  WATER                                      Ex. No.                                                                             % F                                                                              KIT                                                                              RP-2 KIT                                                                              (MIN)                                                                             ABSORB.                                                                             (MIN)                                                                              ABSORB.                                    __________________________________________________________________________    27    0.05                                                                             6  4 × 0                                                                        3  >20 4     >20  4                                                0.07                                                                             8  4 × 0                                                                        3  >20 3     >20  3                                                0.1                                                                              10 4 × 0                                                                        4  >20 4     >20  4                                          28    0.05                                                                             5  4 × 0                                                                        3  <1  96    >20  2                                                0.07                                                                             6  4 × 0                                                                        3  >20 13    >20  4                                                0.1                                                                              8  4 × 0                                                                        4  >20 2     >20  3                                          29    0.05                                                                             4  2 × 100                                                                      3  >20 0     >20  7                                                0.07                                                                             6  2 × 100                                                                      4  >20 8     >20  7                                                0.1                                                                              7  2 × 100                                                                      4  >20 10    > 20 5                                          __________________________________________________________________________

EXAMPLE 31

Synthesis of a di-R_(F) amino-diacid.

A mixture of 13.2 g (89.7 mmol) glutamic acid, 16.0 g (200 mmol, 50%)sodium hydroxide, 16 g deionized water, and 12 g n-propanol is stirredat 50°-55° C. in a three-necked, round-bottomed flask equipped withcondenser, dropping funnel, and stirrer. Then 20.0 g (175 mmol) allylglycidyl ether are added over 20 minutes to give a cloudy, biphasicsystem which, after and additional hour at this temperature, becomesclear and homogeneous. The reaction mixture is stirred for an additional5 hours at 50°-55° C.; then taken to reflux (90° C.) for 30 minutes.Complete consumption of the epoxide is ascertained by gaschromatography.

R_(F) I Addition:

At 30° C., 105.3 g (175 mmol) R_(F) I with a R_(F) -chain lengthdistribution of 1.7% C₆, 49.8% C₈, 33.5% C₁₀, 11.1% C₁₂, 3.1% C₁₄, 0.69%C₁₆ and 0.16% C₁₈, (TEL-AN, from DuPont), 0.7 g (3.6 mmol) VAZO-67, and1.7 g (9 mmol) sodium metabisulfite are charged to the above mixtureunder a nitrogen purge. The slightly yellow, milky mixture is thenheated to 77° C. and the temperature rises to 90° C. After cooling backto 80° C., the white, pasty mixture is stirred for an additional 180minutes. At this time the R_(F) I is completely consumed. Then 16 g (190mmol, 50% ) sodium hydroxide is slowly added to the mixture to eliminateHI. After 60 minutes, the product mixture is cooled to room temperature,poured into 3000 ml cold, deionized water and neutralized with diluteHCl to pH 2-2.5. A precipitate is formed, which is filtered and washed.After drying at 25 mm Hg at 55° C. for one day, 113 g of the product areobtained as a brown solid in 97% yield.

EXAMPLE 32

Synthesis of a di-R_(F) -amino-monoacid.

In a three-necked, 300 ml round-bottomed flask equipped with condenser,thermometer and mechanical stirrer are placed 12.0 g (0.0105 mmol) allylglycidyl ether, 4.7 g (0.0526 mmol β-alanine, 4.2 g (0.0526 mmol, 50%)sodium hydroxide, 4.5 g deionized water and 3.6 g n-propanol. Thetwo-phase mixture is stirred while the temperature is raised to 85° C.After 15 minutes at this temperature, a clear yellow, homogeneous systemis formed. After 2 hours, total consumption of epoxide is determined bygas chromatography and the solution is cooled to 30° C.

To the above solution are charged 63.2 g (0.105 mmol) R_(F) I with aR_(F) -chain length distribution of 1.7% C₆, 49.8% C₈, 33.5% C₁₀, 11.1%C₁₂, 3.1% C₁₄, 0.69% C₁₆ and 0.16% C₁₈, (TEL-AN, from DuPont), 1.0 g(5.26 mmol) sodium metabisulfite, and 0.4 g (2.10 mmol) VAZO-67. Themixture is heated under nitrogen to 75° C. and continues to rise to 90°C. The flask contents are cooled down to 850° C. and stirred at thistemperature for 4 hours. All the R_(F) I is used up as determined by GC.12 g (0.105 mmol, 50%) sodium hydroxide is added to eliminate HI and themixture is stirred for an additional hour. The product mixture is thenpoured into one liter of cold water and acidified with 10% hydrogenchloride. A precipitate is formed which is filtered and dried, first inair at room temperature and then under vacuum to give 63.9 g (96% yield)of a light tan solid.

EXAMPLE 33

The procedure of example 32 is repeated, but using instead ofbeta-alanine an equivalent amount of taurine (2-aminoethylenesulfonicacid). The resulting di-R_(F) -aminosulfonic acid is obtained in 91%yield as a light tan solid, which is soluble in aqueous ammonia.

What is claimed is:
 1. A mono- or disulfate of an alcohol or polyol ofthe formula I or II

    (Q.sub.F --CH.sub.2 O).sub.b --Y--(X).sub.a (I) or Z.sub.e (--L--(U--OH).sub.d).sub.c                                (II)

wherein Q_(F) is Q_(F2), in which Q_(F2) is R_(F) CH═CH--, and R_(F) isa monovalent, straight, branched or cyclic saturated organic radicalhaving 6-18 carbon atoms, which is fully fluorinated and contains atleast one terminal perfluoromethyl group, with each R_(F) radical beingidentical or different from the other R_(F) radicals, Y is a trivalentor tetravalent organic linking group with from 2 to 20 carbon atoms,which can be interrupted by one or more polyvalent groups or heteroatoms selected from --O--, --S--, --N<, --NR₁ --, --CO--, --CONR₁ --,--NHCOO--, --CON<, --CO₂ --, --O₂ C--, --O₂ CO-- and --SO₂ --, in whichR₁ is hydrogen, C₁ -C₂₀ alkyl, di-C₁ -C₂ alkylamino-C₂ -C₆ alkylene,hydroxy-C₁ -C₅ alkylene, or C₁ -C₅ alkyl hydroxy-C₁ -C₅ alkylene, whichis substituted by pyridyl, piperidyl or cyclohexyl, X is OH, O--CH₂--COOH or COOH, a is 1 or 2, b is 2 or 3, L is O, S or NR', in which R'is C₁ -C₂₀ hydrocarbyl, hydroxy-C₂ -C₅ alkylene, carboxymethylene orU--OH. ##STR9## Z is H or a mono-, di-, tri- or tetravelent organicgroup of 1-40 carbon atoms which can be interrupted by one or morepolyvalent groups or hetero atoms selected from --O--, --S--, --N<,--NR₁ --, --CO--, --CONR₁ --, --NHCOO--, --CON<, --CO₂ --, --₂ C--, --O₂CO-- and --SO₂ --, can also be substituted by hydroxyl, carboxyl,carboxyalkyl or sulfonate when L is S or NR', r and q are each,independently, 10 to 10, c is 1 to 4, d is 1 to 3, with the proviso thatwhen c and d are both 1, Z is monovalent and r is >0, and e is 0 or 1,with the proviso that when e is 0, d is 2 and L is S or NR'.
 2. Acompound of the formula I according to claim 1, which is selected fromthe group consisting of mono- and disulfates of alcohols and polyols ofthe formulae (Q_(F2) CH₂ OCH₂)₂ CHOH, (Q_(F2) CH₂ OCH₂)₂ C(CH₂ OH)₂,(Q_(F2) CH₂ OCH₂)₃ C--CH₂ OH and (Q_(F2) CH₂ OCH₂)₂ C(C₂ H₅)CH₂ OH.
 3. Amonosulfate of a diol of the formula II according to claim 1 wherein, inthe definition of U, r is equal to or greater than q and is 0 to 5 and qis 0 to 3, L is O and Z isa) phenyl, p-n-C₁ -C₁₀ alkylphenyl, amonovalent alkyl radical with 1-20 carbon atoms which may be interruptedby --O--, --S-- or --NR₁ -- groups, or is hydroxy-C₂ -C₅ alkylene, or b)1,4-phenylene or a divalent alkylene radical which may be interrupted by--O--, --S-- or --NR_(l) -- groups, or c) a trivalent alkylene radicalwhich may be interrupted by --O--, --S-- or --NR₁ -- groups.
 4. Amonosulfate of a diol or polyol of the formula II according to claim 1wherein, in the definition of U, r is equal to or greater than q and is0 to 5 and q is 0 to 3, anda) L is S and Z is a direct bond or adivalent C₂ -C₂₀ alkylene radical which may be interrupted by --O-- or--NR₁ --, or b) L is NR', R' is U--OH and Z is a divalent alkyleneradical with 2 to 12 carbon atoms which be interrupted by --O--, --S--or --NR₁ -- groups and substituted by hydroxy or carboxy groups.
 5. Amonosulfate of a diol or polyol of the formula II according to claim 1wherein, in the definition of U, r is equal to or greater than q and is0 to 5 and q is 0 to 3, L is O and Z is --CH₂ CH₂ --, or a monosulfateof a polyol of the formula CH₃ CH₂ --C--(CH₂ OCH₂ CH(OH)CH₂ OCH₂Q_(F2))₃ or (HOCH₂)₂ (C₂ H₅)--C--N(CH₂ OCH₂ CH(OH)CH₂ OCH₂ Q_(F2))₂.